Electrochemical Rectification of Redox Mediators Using Porphyrin-Based Molecular Multilayered Films on ITO Electrodes

Electrochemical charge transfer through multilayer thin films of zinc and nickel 5,10,15,20-tetra­(4-ethynylphenyl) porphyrin constructed via copper­(I)-catalyzed azide–alkyne cycloaddition (CuAAC) “click” chemistry was examined. Current rectification toward various outer-sphere redox probes is revealed with increasing numbers of layers, as these films possess insulating properties over the neutral potential range of the porphyrin, then become conductive upon reaching its oxidation potential. Interfacial electron transfer rates of mediator–dye interactions toward [Co­(bpy)₃]²⁺, [Co­(dmb)₃]²⁺, [Co­(NO₂-phen)₃]²⁺, [Fe­(bpy)₃]²⁺, and ferrocene (Fc), all outer-sphere redox species, were measured by hydrodynamic methods. The ability to modify electroactive films’ interfacial electron transfer rates, as well as current rectification toward redox species, has broad applicability in a number of devices, particularly photovoltaics and photogalvanics.